(Co)polymers based on vinyl units and use thereof in electroluminescent devices

ABSTRACT

This invention relates to (co)polymers which contain at least one repeat chain unit of the general formula (1) or (2) and optionally contain repeat units of the general formula (3)  
                 
 
     in which  
     L 1  and L 2  mean a photoluminescent residue,  
     wherein the proportion of structural units of the formulae (1) and/or (2) is in each case 0.5 to 100 mol.%, and (3) 0 to 99.5 mol.%, and the molar percentages add up to 100,  
     to the use thereof for the production of electroluminescent devices and to the electroluminescent devices.

[0001] Light-emitting components for electronics and photonics are todaymainly developed using inorganic semiconductors, such as galliumarsenide. Punctual display elements may be produced using suchsubstances. Devices of a large area are not possible.

[0002] In addition to semiconductor light emitting diodes,electroluminescent devices based on vapour-deposited low molecularweight organic compounds are also known (U.S. Pat. No. 4,539,507, U.S.Pat. No. 4,769,262, U.S. Pat. No. 5,077,476P). With these materials too,as a consequence of the production process, it is only possible toproduce small LEDs. Furthermore, these electroluminescent devices haveelevated production costs and only a very short service life.

[0003] Polymers such as poly(p-phenylenes) andpoly(p-phenylene-vinylenes) are described as electroluminescent: Adv.Mater. 4 (1992) no. 1; J. Chem. Soc., Chem. Commun. 1992, pages 32-34;Polymer, 1990, volume 31, 1137; Physical Review B, volume 42, no. 18,11670 or WO 90/13148.

[0004] In contrast to the fully conjugated polymers, non fullyconjugated polycondensation products with luminescent structural unitsare described in electroluminescent devices (Macromol. Chem. Phys. 195,2023-2037 (1994)).

[0005] The present invention provides polymers for the production ofelectroluminescent devices, which polymers are based on a well knownbasic structure, such as polystyrene and polyacrylate, with covalentlybonded luminophoric units in the side chains. Due to their simpleproduction process and ready processability, such polymers are of greattechnical interest with regard to use as electroluminescent materials.Electroluminescent devices containing these (co)polymers aredistinguished by elevated light intensities and a broad range of colourhues. The advantages of the (co)polymers according to the invention are,for example, that

[0006] 1. light intensity may purposefully be modified by varying theconcentration of luminophore,

[0007] 2. colour hues may be adjusted by combining different monomerscontaining luminophores,

[0008] 3. the morphology and electrical properties of the polymer layersmay be optimised by the incorporation of suitable side chain units.

[0009] The present invention relates to (co)polymers which contain atleast one repeat chain unit of the general formula (1) or (2) andoptionally contain repeat units of the general formula (3)

[0010] in which

[0011] R¹, R² and R³ mutually independently mean hydrogen or C₁-C₆alkyl,

[0012] M denotes CN or C₁-C₃₀ alkoxycarbonyl, C₁-C₃₀(di)alkyl-aminocarbonyl, C₁-C₃₀ alkylcarbonyl, which may each besubstituted by hydroxy or C₁-C₆ alkoxycarbonyl, and furthermore denotesphenyl, naphthyl, anthracenyl, pyridyl or carbazolyl, which may each besubstituted by residues from the group halogen, hydroxy, silyl, C₁-C₃₀alkyl, C₆-C,₈ aryl, C₁-C₃₀ alkoxy, C₁-C₃₀ alkoxycarbonyl, C₁-C₃₀ acyloxyand C₁-C₃₀ alkylcarbonyl,

[0013] L¹ and L² mean a photoluminescent residue,

[0014] wherein the proportion of structural units of the formula (3) is0 to 99.5, preferably 40 to 99.5 mol.% and the proportion of structuralunits (1) and/or (2) is in each case 0.5 to 100, preferably 0.5 to 60mol.% and the molar proportions add up to 100%.

[0015] In the above-stated formulae, R¹, R² and R³ mutuallyindependently preferably mean hydrogen, methyl or ethyl.

[0016] M preferably denotes CN or C₁-C₁₅ alkoxycarbonyl, C₁-C₁₅(di)alkylaminocarbonyl, C₁-C₁₅ alkylcarbonyl, which may each besubstituted by hydroxy or methoxycarbonyl, ethoxycarbonyl, n- oriso-propoxycarbonyl, and furthermore denotes phenyl, naphthyl,anthracenyl, pyridyl or carbazolyl, which may each be substituted byresidues from the group chlorine, bromine, hydroxy, silyl, C₁-C₆ alkyl,C₁-C₆ alkoxy, C₁-C₆ alkoxycarbonyl, C₁-C₆ acyloxy and C₁-C₆alkylcarbonyl, phenyl optionally substituted by methyl, ethyl, n- oriso-propyl.

[0017] L¹ and L² mutually independently denote a photoluminescentresidue which is based on the skeleton of a fluorescent dye which isselected from the group of coumarins of the formula (4)

[0018] pyrenes of the formula (5)

[0019] 1,8-naphthalimides of the formula (6)

[0020] 1,8-naphthaloylene-1,2-benzimidazoles of the formulae (7a) and(7b)

[0021] phenothiazines or phenoxazines of the formula (8)

[0022] with X¹=O or S,

[0023] benzopyrones of the formula (9)

[0024] carbazoles, fluorenes, dibenzothiophenes and -furans of theformula (10)

[0025] with X²=NR²³, CH₂, S or O, wherein R²³ denotes hydrogen or C₁-C₆alkyl, preferably hydrogen or C₁-C₄ alkyl,

[0026] oxazoles, 1,3,4-oxadiazoles of the formula (11)

[0027] with X³=CH or N

[0028] benzoquinolines of the formula (12)

[0029] 9,10-bis-(phenylethynyl)anthracenes of the formula (13)

[0030] fluorones of the formula (14)

[0031] 9,10-diphenylanthracene of the formula (15)

[0032] 2-styrylbenzazole of the formula (16)

[0033] with X⁴=O, S, Se or CH₂,

[0034] wherein

[0035] R⁴ denotes hydrogen, C₁-C₃₀ alkyl, C₆-C₁₈, aryl, C₇-C₂₄ aralkylor C₁-C₃₀ alkoxy or

[0036] wherein

[0037] R⁴³ and R⁴⁴ mutually independently denote hydrogen, C₁-C₃₀ alkyl,C₆-C₁₈ aryl, C₇-C₂₄ aralkyl, which may each be substituted by hydroxy,amino, carboxy or C₁-C₄ alkoxycarbonyl, or

[0038] R⁴³ and R⁴⁴, together with the nitrogen atom to which they areattached, may mean a morpholine, piperidine, pyrrolidine or piperazinering, which may bear one or two substituents from the group methyl,ethyl and phenyl,

[0039] R⁵ denotes hydrogen, cyano, C₁-C₃₀ alkyl, C₆-C₁₈ aryl, C₇-C₂₄aralkyl, C₁-C30 alkoxy, C₂-C₁₂ acyl, C₁-C₁₂ alkoxycarbonyl, C₁-C₁₂(di)alkylaminocarbonyl,

[0040] R⁶ denotes hydrogen, cyano, C₁-C₃₀ alkyl, C₆-C, aryl, C₇-C₂₄aralkyl, C₁-C₃₀ alkoxy or

[0041] wherein Z denotes a group OR⁴⁵ or

[0042] R⁴⁵, R⁴⁶ and R⁴⁷ mutually independently denote C₁-C₃₀ alkyl,C₆-C₁₈ aryl or C₇-C₂₄ aralkyl, wherein the aromatic rings mayadditionally be further substituted by halogen, C₁-C₆ alkyl, C₁-C₆alkoxy,

[0043] R⁷, R⁸ and R⁹ mutually independently mean hydrogen, C₁-C₃₀ alkyl,C₆-C₁₈ aryl, C₇-C₂₄ aralkyl, C₁-C₃₀ alkoxy, cyano, C₂-C₁₂ acyl, C₁-C₁₂alkoxycarbonyl, C₁-C₁₂ (di)alkyl-aminocarbonyl or an amino group withone or two C₁-C₆ alkyl groups,

[0044] R¹⁰ means hydrogen, cyano, C₁-C₃₀ alkyl, C₆-C₁₈ aryl, C₇-C₂₄aralkyl, C₁-C₃₀ alkoxy, amino, C₂-C₁₂ acyl, C₁-C₁₂ alkoxycarbonyl,C₁-C₁₂ (di)alkylaminocarbonyl,

[0045] R¹¹ denotes hydrogen, halogen, nitro, C₁-C₄ alkoxycarbonyl, C₁-C₄acyl, C₈-C₂₄ aralkenyl, unsubstituted amino, or amino identically ordifferently mono- or disubstituted by C₁-C₃₀ alkyl, C₆-C₁₈ aryl orC₇-C₂₄ aralkyl,

[0046] R¹¹ furthermore denotes morpholinyl, piperidinyl, pyrrolidinyl orpiperazinyl, which may bear one or two substituents selected frommethyl, ethyl and/or phenyl,

[0047] R¹² denotes hydrogen, C₁-C₃₀ alkyl, C₆-C₁₈ aryl, C₇-C₂₄ aralkylor C₁-C₃₀ alkoxy,

[0048] R¹³ denotes hydrogen, C₁-C₃₀ alkyl, C₆-C₁₈ aryl, C₇-C₂₄ aralkyl,C₁-C₃₀ alkoxy or

[0049] wherein

[0050] R⁴⁹ and R⁵⁰ mutually independently denote C₁-C₃₀ alkyl, C₆-C₁₈aryl, C7-C₂₄ aralkyl or

[0051] R⁴⁹ and R⁵⁰, together with the nitrogen atom to which they areattached, moreover denote a morpholinyl, piperidinyl, pyrrolidinyl orpiperazinyl, which may bear one or two identical or differentsubstituents selected from methyl, ethyl and phenyl,

[0052] R¹⁴ and R¹⁵ mutually independently mean hydrogen, cyano, halogen,nitro, C₁-C₃₀ alkyl, C₁-C₃₀ alkoxy, C₆-C₁₈ aryl or C₇-C₂₄ aralkyl,C₁-C₁₂ alkoxycarbonyl, C₂-C₁₂ acyl, C₁-C₁₂ (di)alkylaminocarbonyl, C₁-C₆(di)alkylamino,

[0053] R¹⁷ and R²³ mutually independently mean hydrogen, C₁-C₃₀ alkyl,C₆-C₁₈ aryl or C₇-C₂₄ aralkyl and

[0054] R¹⁶, R¹⁸ to R²³ and R²⁴ to R⁴⁰ mutually independently meanhydrogen, cyano, C₁-C₃₀ alkyl, C₆-C₁₈ aryl, C₇-C₂₄ aralkyl, C₁-C₃₀alkoxy, an amino group with one or two C₁-C₆ alkyl groups, unsubstitutedamino, C₂-C₁₂ acyl, C₁-C₁₂ alkoxycarbonyl or C₁-C₁₂(di)alkylaminocarbonyl, wherein the aliphatic carbon chains, such as,for example, alkyl, alkoxy, alkylamino, aralkyl, in the residues R⁴ toR¹³, R¹⁶ to R⁴⁰ may be interrupted by one or more, preferably one or twoheteroatoms selected from oxygen, nitrogen and sulphur and/or by one ormore, preferably one or two, phenylene rings, which may be substitutedby C₁-C₄ alkyl and/or halogen,

[0055] and wherein furthermore the luminophore is attached to thepolymer side chains via an oxygen, a hydroxy or carboxy group or anitrogen of an amino or primary amino on the above-stated substituents.

[0056] In the above-stated residues R⁴ to R⁴⁰, at least one aliphatic,aromatic or heterocyclic carbon chain per fluorescent dye bears at leastone hydroxy, carboxy or optionally an amino group, preferably hydroxy,by means of which the covalent bond to the monomer is formed by thereaction of these groups with a reactive group (for example halogen)located on the monomer, c.f. production process. In the case of monomer(1), this attachment site is the methylene group on the phenyl ring(—CH₂—Cl reacts). In the case of monomer (2), the attachment site is thecarbonyl group (via —CO—Cl).

[0057] M in particular denotes phenyl, naphthyl, anthracenyl, pyridyl orcarbazolyl, which may each be substituted by hydroxy, silyl, C₁-C₄alkyl, optionally by phenyl substituted by methyl, ethyl, n- oriso-propyl, by C₁-C₄ alkoxy, C₁-C₆ alkoxycarbonyl, C₁-C₆ acyloxy orC₁-C₆ alkylcarbonyl.

[0058] L¹ and L² in particular mutually independently denote afluorescent dye residue selected from the group of coumarins of theformula (4), pyrenes of the formula (5), 1,8-naphthalimides of theformula (6), 1,8-naphthaloylene-1,2-benzimidazoles of the formula (7),phenothiazines or phenoxazines of the formula (8), carbazoles andfluorenes of the formula (10).

[0059] R⁴ preferably presents C₁-C₆ alkyl, C₆-C₁₀ aryl or C]-C₆ alkoxyor

[0060] wherein

[0061] R⁴³ and R⁴⁴ preferably independently represent C₁-C₆ alkyl,C₆-C₁₀ aryl which may each be substituted by hydroxy and/or amino or

[0062] R⁴³ and R⁴⁴ together with the nitrogen atom to which they areattached may mean a morpholine, piperidine, pyrrolidine or piperazinering which may bear one or two substituents from the group methyl, ethyland phenyl.

[0063] R⁵ preferably denotes hydrogen or cyano,

[0064] R⁶ preferably denotes hydrogen, C₁-C₆ alkyl, C₆-C₁₀ aryl oderC₁-C₆ alkoxy or

[0065] wherein Z denotes a group OR⁴⁵ or

[0066] and

[0067] R⁴⁵, R⁴⁶ and R⁴⁷ independently preferably represent C₁-C₆ alkylor C₆-C₁₀ aryl, in particular phenyl or naphthyl,

[0068] R⁷, R⁵ and R⁹ independently preferably represent hydrogen, C₁-C₆alkyl, C₆-C₁O aryl, C₁-C₆ alkoxy or cyano,

[0069] R¹⁰ preferably denotes hydrogen, cyano, C₁-C₆ alkyl, C₆-C₁₀ aryl,in particular phenyl or naphthyl, C₂-C₄ acyl oder C₁-C₆ alkoxycarbonyl,

[0070] R¹¹ preferably denotes hydrogen, halogen, nitro, C₁-C₄alkoxycarbonyl, C₁-C₄ acyl, C₈-C₂₄ aralkenyl or amino identically ordifferently mono- or disubstituted by C₁-C₆ alkyl, C₆-C₁₀ aryl, inparticular phenyl or naphthyl,

[0071] R¹¹ furthermore denotes morpholinyl, piperidinyl, pyrrolidinyl orpiperazinyl which may bear one or two substituents selected from methyl,ethyl or phenyl,

[0072] R¹² preferably denotes C₁-C₆ alkyl, C₆-C₁₀ aryl, in particularphenyl or naphthyl, or C₇-C₁₂ aralkyl.

[0073] R¹³ preferably denotes hydrogen, C₁-C₆ alkyl, C₆-C₁₀ aryl, inparticular phenyl or naphthyl, or C₁-C₆ alkoxy or

[0074] wherein

[0075] R⁴⁹ and R⁵⁰ independently preferably denote C₁-C₆ alkyl, C₆-C₁₀aryl, in particular phenyl or naphthyl, or

[0076] R⁴⁹ und R⁵⁰ together with the nitrogen atom to which they areattached, moreover denote a morpholinyl, piperidinyl, pyrrolidinyl orpiperazinyl, which may bear one or two identical or differentsubstituents selected from methyl, ethyl and phenyl,

[0077] R¹⁴ and R¹⁵ independently preferably represent hydrogen, cyano,halogen, nitro, C₁-C₆ alkyl, C₁-C₆ alkoxy, C₆-C₁₀ aryl, in particularphenyl or naphthyl,

[0078] R¹⁷ and R²³ independently preferably represent hydrogen, C₁-C₆alkyl, C₆-C₁₀ aryl.

[0079] R¹⁶, R¹⁸ to R²² and R²⁴ to R⁴⁰ independently preferably representhydrogen, cyano, C₁-C₆ alkyl, C₆-C₁₀ aryl, C₁-C₆ alkoxy, aminosubstituted by one or two C₁-C₆ alkyl groups, unsubstituted amino,

[0080] wherein the aliphatic carbon chains such as e.g. alkyl, alkoxy,Alkylamino, aralkyl, in the residues of R⁴ to R¹³, R¹⁶ to R⁴⁰ may beinterrupted by a heteroatom, selected from oxygen, nitrogen and sulphurand/or a phenyl ring.

[0081] Alkyl residues, for example, in alkyl, alkoxy, alkoxycarbonyl or(di)alkylamino are exemplified by methyl, ethyl, n- or iso-propyl, n-,iso- or tert.-butyl. Aryl represents in particular phenyl and naphthyl.Aralkyl represents in particular phenyl-C₁-C₄-alkyl, z.B. phenylmethyl,phenylethyl or naphthyl-C₁-C₄-alkyl, e.g. naphthylmethyl, naphthylethyl.

[0082] The present invention furthermore relates to a process for theproduction of the above-stated (co)polymers which contain at least onerepeat chain unit of the general formula (1) or (2) and optionallyrepeat units of the general formula (3),

[0083] wherein the residues have the above-stated meanings,

[0084] wherein the corresponding monomers of the formula (20) or (21)are produced

[0085] from a fluorescent dye functionalised with an OH, COOH or NHgroup, which dye contains the structure of L,

[0086] and a styrene or acrylic acid derivative of the formulae (22) and(23)

[0087] in which

[0088] R¹ and R² have the above-stated range of meaning and

[0089] R⁴¹ denotes a halogen atom, preferably Cl or Br,

[0090] R⁴² denotes a halogen atom, preferably Cl or Br, a hydroxy orC₁-C₆ alkoxy group,

[0091] in the presence of a base, preferably triethylamine, pyridine oran alkali metal alkoxide and these monomers are then polymerised,optionally in the presence of units of the formula (3) as comonomers.

[0092] The reaction of the fluorescent dyes functionalised with an OH,carboxyl or NH group generally proceeds at temperatures of −30° C. to100° C., preferably from 0° C. to 60° C.

[0093] Polymerisation processes are described in the literature. Theymay proceed by ionic or free-radical polymerisation. Anionicpolymerisation may, for example, be initiated by initiators such asbutyllithium or lithiumnapthalide. Free-radical polymerisation may beinitiated by, for example, free-radical initiators, such as for exampleazo initiators or peroxides, preferably AIBN (azoisobutyro-nitrile) ordibenzoyl peroxide. The polymers may be produced using bulk methods orin suitable solvents such as benzene, toluene, tetrahydrofuran, dioxane,ethyl acetate, xylene, chlorobenzene, 1-methoxy-2-propyl acetate,chlorinated hydrocarbons, acetone etc., at temperatures of 20-250° C.

[0094] Production of the (co)polymers according to the invention isillustrated by way of example by the following reaction scheme:

[0095] In this scheme, the methacrylate (26) is initially producedstarting from 3-(6-hydroxyhexoxycarbonyl)-7-diethylamino-coumarin (24)and methacryloyl chloride (25) together with triethylamine at 0° C. toroom temperature. The methacrylate (26) may be polymerised inchlorobenzene at 100° C. in the presence of n-butyl acrylate (27) as acomonomer together with AIBN as free-radical initiator to form thecopolymer (28). The preferred molar percentage x of comonomer (26) isbetween 0.5 and 60%.

[0096] Production of the polymers or copolymers according to theinvention may furthermore be illustrated by way of example by thefollowing reaction scheme:

[0097] In this scheme, the styrene derivative (31) is first produced at0° C. to room temperature in a phase transfer catalysed reactionstarting from phenothiazine (29) and m/p-vinylbenzene chloride (30)together with sodium hydroxide and tributylammonium hydrogen sulphite ina catalytic quantity. The styrene derivative (31) may be polymerised intoluene at 80° C. to 100° C. in the presence of m/p-methylstyrene (32)as comonomer together with AIBN as free-radical initiator to form thecopolymer (33). The preferred molar percentage x of comonomer (31) isbetween 0.5 and 60%.

[0098] Production of the polymers or copolymers according to theinvention may furthermore be illustrated by way of example by thefollowing reaction scheme:

[0099] In this scheme, the methacrylate (35) is first produced at 0° C.to room temperature starting from4/5-(N-methyl-N-hydroxyethyl)amino-1,8-naphthoylene- 1′,2′-benzimidazole(34) (only 4-isomer shown) and methacryloyl chloride (25) together withtriethylamine. The methacrylate (35) may be polymerised in chlorobenzeneat 80° C in the presence of N-vinylcarbazole (36) as comonomer togetherwith AIBN as free-radical initiator to form the copolymer (37). Thepreferred molar percentage x of comonomer (35) is between 0.5 and 60%.

[0100] Production of the polymers or copolymers according to theinvention may furthermore be illustrated by way of example by thefollowing reaction scheme:

[0101] In this scheme, the styrene derivative (39) is first produced atroom temperature in tetrahydrofuran starting fromN-isoamyl-4-(N-methyl-N-hydroxyethyl)amino-1,8-naplithalimide (38) andmip-vinylbenzyl chloride (30) together with potassium tert.-butylate.The styrene derivative (39) may be polymerised in toluene at 100° C.together with AIBN as free-radical initiator to form the homopolymer(40).

[0102] The styrene derivative (39) may also be copolymerised with acomonomer such as, for example, N-vinylcarbazole, styrene, n-butylacrylate etc..

[0103] (Co)polymers of the present invention have molecular weights,determined by gel permeation chromatography, in the range from 500 to 1million g/mol, preferably of 800 to 500000 g/mol.

[0104] Some of the fluorescent dyes functionalised with OH, SH or NH(c.f. definition of residue L), which are necessary for the productionof the (co)polymers according to the invention, are known.

[0105] The coumarin derivatives of the following formula (4a) are novel:

[0106] wherein

[0107] R⁴³ and R⁴⁴ mutually independently denote hydrogen, C₁-C₃₀ alkyl,C₆-C₁₈ aryl, C₇-C₂₄ aralkyl, which may each be substituted by hydroxy,amino, carboxy or C₁-C₄ alkoxycarbonyl or

[0108] R⁴³ and R⁴⁴, together with the nitrogen atom to which they areattached, may mean a morpholine, piperidine, pyrrolidine or piperazinering, which may bear one or two substituents from the group methyl,ethyl and phenyl, and

[0109] Z denotes a group OR⁴⁵ or

[0110] wherein

[0111] R⁴⁵ means C₁-C₃₀ alkyl, C₆-C₁₈ aryl or C₇-C₂₄ aralkyl, which areeach substituted by at least one hydroxy group and wherein the aromaticrings may additionally be substituted by halogen, C₁-C₆ alkyl C₁-C₆alkoxy and

[0112] R⁴⁶ and R⁴⁷ mutually independently denote C₁-C₃₀ alkyl C₆-C₁₈aryl or C₇-C₂₄ aralkyl, each optionally hydroxy-substituted, wherein atleast one of the residues R⁴⁶ or R⁴⁷ has a hydroxy group and wherein thearomatic rings may additionally be substituted by halogen, C₁-C₆ alkyl,C₁-C₆ alkoxy.

[0113] The coumarin derivatives of the formula (4a) according to theinvention bear at least one hydroxy group by means of which they may bechemically bonded to the polymer side chains.

[0114] In the formula (4a), R⁴³ and R⁴⁴ mutually independentlypreferably denote hydrogen or C₁-C₁₆ alkyl, optionally substituted byhydroxy, amino, carboxy and/or C₁-C₄ alkoxycarbonyl, each unsubstituted,or phenyl, naphthyl, phenyl-C₁-C₄-alkyl or naphthyl-C₁-C₄-alkylsubstituted by C₁-C₄ alkyl, hydroxy, amino, carboxy, C₁-C₄alkoxycarbonyl, chlorine and/or bromine.

[0115] R⁴³ and R⁴⁴ in particular denote C₁-C₆ alkyl or phenyl optionallysubstituted by hydroxy, amino or carboxy,

[0116] Z in the above-stated formula (4a) denotes OR⁴⁵ or NR⁴⁶R⁴⁷,wherein R⁴⁵ preferably denotes C₁-C₁₆ alkyl, phenyl, naphthyl,phenyl-C₁-C₄-alkyl or naphthyl-C₁-C₄-alkyl, which are each substitutedby at least one hydroxy group, and wherein the aromatic rings mayadditionally be substituted by halogen, C₁-C₆ alkyl, C₁-C₆ alkoxy,

[0117] R⁴⁶ and R⁴⁷ mutually independently preferably denote C₁-C₁₆alkyl, phenyl, naphthyl, phenyl-C₁-C₄-alkyl or naphthyl-C₁-C₄-alkyl,each optionally substituted by hydroxy, wherein at least one of theresidue R⁴⁶ or R⁴⁷ has a hydroxy group and the aromatic rings mayadditionally also be substituted by halogen, C₁-C₆ alkyl C₁-C₆ alkoxy

[0118] R⁴⁵ particularly preferably denotes a C₁-C₁₂ alkyl substituted bya hydroxy group.

[0119] R⁴⁶ and R⁴⁷ mutually independently particularly preferably denoteC₁-C₁₂ alkyl optionally substituted by a hydroxy group, wherein at leastone of the residues R⁴⁶ and R⁴⁷ has a hydroxy group.

[0120] The novel coumarin derivatives of the formula (4a),

[0121] wherein R⁴³, R⁴⁴ and Z have the above-stated meaning, may beproduced by,

[0122] a) in the event that Z denotes —OR⁴⁵, producing the malonic acidderivative of the formula (III)

[0123] preferably in a single vessel process from the Meldrums acid ofthe formula (I)

[0124] and an alcohol of the formula (II)

R⁴⁵—OH  (II)

[0125] optionally in the presence of a diluent, such as for exampletoluene, xylene or mesitylene with catalysis by, for example,p-toluenesulphonic acid at temperatures in the range from 20 to 250° C.,preferably from 80 to 150° C.,

[0126] and then reacting this malonic acid derivative with a salicylicaldehyde of the formula (IV)

[0127] wherein R⁴³, R⁴⁴, R⁴⁵ have the above-stated meaning,

[0128] optionally in the presence of a diluent, such as for exampletoluene, xylene, mesitylene, with catalysis by, for example, piperidineacetate at temperatures of 50 to 250° C., preferably of 80 to 140° C.,and,

[0129] b) in the event that Z denotes

[0130] by reacting a salicylic aldehyde of the formula (IV), a secondaryamine of the formula (V) and a malonic acid derivative of the formula(VI)

[0131] in which

[0132] R⁴³, R⁴⁴, R⁴⁶ and R⁴⁷ have the above-stated meaning and

[0133] R⁴⁸ denotes C₁-C₆ alkyl,

[0134] optionally in the presence of a diluent, such as for exampletoluene, xylene or mesitylene, with catalysis by, for example,piperidine acetate at temperatures of 50 to 250° C., preferably of 80 to140° C.

[0135] When performing the process a) according to the invention, 2-10mol, preferably 3-6 mol of alcohol of the formula (1I) are generallyused for each mol of Meldrums acid, and 0.5-1.0, preferably 0.9-1.0 molof salicylic aldehyde of the formula (IV) is generally used for each molof malonic acid derivative of the formula (III).

[0136] When performing the process b) according to the invention, 2-20,preferably 5-10 mol of secondary amine and 1-2, preferably 1.2-1.5 molof malonic acid derivative of the formula (VI) are generally used permol of salicylic aldehyde of the formula (IV).

[0137] Production of the coumarin derivatives of the formula (4a)according to the invention, where Z=OR⁴⁵, by way of a Knoevenagelcondensation reaction and subsequent cyclisation is illustrated by wayof example by the following reaction scheme:

[0138] In this scheme, bis-(6-hydroxyhexyl) malonate is first producedby reacting the Meldrums acid and 1,6-hexanediol in the presence ofcatalytic quantities of p-toluene-sulphonic acid with elimination ofacetone and water. The bis-(6-hydroxyhexyl) malonate is then combinedwith 4-diethylaminosalicylic aldehyde in the presence of catalyticquantities of piperidine acetate to form the desired3-(6-hydroxyhexoxycarbonyl)-7-diethylaminocoumarin.

[0139] Production of the coumarin derivatives of the formula (4a)according to the invention, where Z=NR⁴⁶R⁴⁷, is illustrated by way ofexample by the following reaction scheme:

[0140] In this scheme, 4-diethylaminosalicylic aldehyde is reacted withdiethyl malonate and 2-(methylamino)ethanol in the presence of catalyticquantities of piperidine acetate. The desired3-[(N-hydroxyethyl-N-methyl)aminocarbonyl]-7-diethylamnino-coumarin isobtained.

[0141] The starting products of the formulae (I), (II), (III), (IV), (V)and (VI) are compounds which are generally known in organic chemistry.

[0142] The following 1,8-naphthalimide derivatives of the formulae (6a),(7a-1) and (7b-1) are also novel:

[0143] in which

[0144] R^(11′) denotes hydrogen, halogen, nitro, C₁-C₄ alkoxycarbonyl,C₁-C₄ acyl, C₈-C₂₄ aralkenyl, unsubstituted amino or amino identicallyor differently mono- or disubstituted by C₁-C₃₀ alkyl, C₆-C₁₈ aryl,C₇-C₂₄ aralkyl, wherein the above-stated carbon chains may themselves besubstituted by hydroxy and/or carboxy,

[0145] R^(11′) furthermore denotes morpholinyl, piperidinyl,pyrrolidinyl or piperazinyl, which may bear one or two substituentsselected from methyl, ethyl and/or phenyl,

[0146] R^(12′) denotes hydrogen or C₁-C₃₀ alkyl, C₁-C₃₀ alkoxy, C₆-C₁₈aryl, C₇-C₂₄ aralkyl, which may be mono- or polysubstituted by hydroxyand/or carboxy,

[0147] and at least one of the residues R¹¹ or R¹² has a hydroxy orcarboxy group,

[0148] R^(49′) and R^(50′) mutually independently denote C₁-C₃₀ alkyl,C₆-C₁₈ aryl, C₇-C₂₄ aralkyl, which may be substituted by hydroxy,wherein at least one of the residues R⁴⁹ or R^(50′) has a hydroxy orcarboxy group.

[0149] R^(49′) and R^(50′), together with the nitrogen atom to whichthey are attached, moreover denote morpholinyl, piperidyl, pyrrolidyl orpiperazinyl, which may bear one or two identical or differentsubstituents selected from methyl, ethyl and phenyl and have at last onehydroxy or carboxy group,

[0150] R¹⁴ and R¹⁵ mutually independently mean hydrogen, halogen, cyano,nitro, C₁-C₃₀ alkyl, C₁-C₃₀ alkoxy, C₆-C₁₈ aryl, C₇-C₂₄ aralkyl, C₁-C₁₂alkoxycarbonyl, C₂-C₁₂ acyl or C₁-C₆ (di)alkylamino.

[0151] The 1,8-naphthalimide derivatives of the formulae (6a), (7a-1)and (7b-1) according to the invention bear at least one hydroxy or onecarboxy group, preferably a hydroxy group, by means of which they may bechemically bonded to the polymer side chains.

[0152] In the above-stated formula (6a),

[0153] R^(11′) preferably denotes hydrogen, chlorine, bromine, nitro,methoxycarbonyl, ethoxycarbonyl, n- or iso-propoxy-carbonyl,methylcarbonyl, ethylcarbonyl, n- or iso-propylcarbonyl, amino, aminoidentically or differently mono- or disubstituted by C₁-C₁₅ alkyl,phenyl, naphthyl, phenyl-C₁-C₄-alkyl or naphthenyl-C₁-C₄-alkyl, in eachcase optionally substituted by methyl and/or ethyl, wherein theabove-stated carbon chains may themselves by substituted by hydroxy,R^(11′) furthermore preferably denotes morpholinyl, piperidinyl,pyrrolidinyl or piperazinyl, which may bear one or two substituentsselected from hydroxy, methyl, ethyl and/or phenyl.

[0154] R^(12′) preferably denotes C₁-C₁₅ alkyl, phenyl orphenyl-C₁-C₆-alkyl, which may be substituted by hydroxy and the aromaticrings may additionally be substituted by halogen, C₁-C₆ alkyl and/orC₁-C₆ alkoxy.

[0155] R^(11′) in particular denotes chlorine, bromine, amino which isidentically or differently mono- or disubstituted by C₁-C₁₅ alkyl,morpholinyl, piperidinyl, pyrrolidinyl or piperazinyl, wherein theabove-stated carbon chains may themselves by substituted by hydroxy.

[0156] R^(12′) in particular denotes C₁-C₁₂ alkyl, phenyl optionallysubstituted by halogen, C₁-C₆ alkyl, C₁-C₆ alkoxy, which may bear ahydroxy group.

[0157] At least one of the residues R^(11′) and R^(12′) must have ahydroxy group.

[0158] R^(49′) and R^(50′) in the formulae (7a-1) and (7b-1) mutuallyindependently preferably denote C₁-C₁₅ alkyl, phenyl,phenyl-C₁-C₆-alkyl, naphthyl, naphthyl-C₁-C₆-alkyl, which may be mono-or poly-, in particular monosubstituted by hydroxy, wherein at least oneof the residues R^(49′) or R^(50′) has a hydroxy group.

[0159] R^(49′) and R^(50′), together with the nitrogen atom to whichthey are attached, moreover preferably denote piperidinyl orpiperazinyl, which may bear one or two identical or differentsubstituents selected from methyl, ethyl and phenyl and have at leastone hydroxy or carboxy group,

[0160] R¹⁴ and R¹⁵ in the formulae (7a-1) and (7b-1) mutuallyindependently preferably denote hydrogen, halogen, C₁-C₁₅ alkyl, C₁-C₁₅alkoxy, C₁-C₄ alkoxycarbonyl, C₁-C₄ acyl or di(C₁-C₆-alkyl)amino,phenyl, phenyl-C₁-C₆-alkyl, naphthyl or naphthyl-C₁-C₆-alkyl in eachcase substituted by methyl and/or ethyl.

[0161] R^(49′) and R^(50′) in particular denote C₁-C₁₂ alkyl, phenyl,phenyl-C₁-C₆ alkyl, which may be substituted by a hydroxy group, whereinat least one of the residues R^(49′) or R^(50′) has a hydroxy group.

[0162] R¹⁴ and R¹⁵ in particular denote hydrogen, halogen, C₁-C₁₂ alkyl,C₁-C₁₂ alkoxy, di(C₁-C₆-alkyl)amino, phenyl.

[0163] The number of hydroxy groups and/or carboxy groups is at leastone, but there may also be up to four hydroxy and/or carboxy groups.

[0164] The aromatic rings in the above-stated residues may beidentically or differently mono- to penta-, preferably mono- totrisubstituted by the stated substituents.

[0165] The aliphatic carbon chains, such as for example alkyl, alkoxy,alkylamino, aralkyl in R⁴³, R⁴⁴, R⁴⁵, R⁴⁶ and R⁴⁷, R^(11′), R^(12′),R^(45′), R^(50′) may be interrupted by one or more, preferably one ortwo heteroatoms selected from oxygen, nitrogen and sulphur, and/or byone or more, preferably one or two phenylene rings, which may besubstituted by C₁-C₄ alkyl and/or halogen.

[0166] A process for the production of novel 1,8-naphthalimidederivatives of the formula (6a)

[0167] in which

[0168] R^(11′) and R^(12′) have the above-stated meaning,

[0169] is characterised in that either

[0170] a) a 1,8-naphthalic anhydride of the formula (VII) and a primaryamine of the formula (VIII),

[0171] are reacted together at 50 to 250° C., preferably at 90 to 140°C., optionally in the presence of diluents, such as for example aceticacid, butanol, chlorobenzene, toluene or xylene or,

[0172] b) in the event that R^(11′) in formula (6a) means anunsubstituted, mono- or disubstituted amino or cyclic amino, a1,8-naphthalimide of the formula (6a-1)

[0173] in which

[0174] R^(11′) denotes halogen, preferably chlorine, bromine or iodine,or nitro,

[0175] which is produced from a 1,8-naphthalic anhydride of the formula(VIIA) and a primary amine of the formula (VIII)

[0176] in which R^(11′) and R^(12′) have the above stated meaning,

[0177] at temperatures of 50 to 250° C., preferably of 90 to 140° C.,optionally in the presence of diluents, such as for example acetic acid,butanol, chlorobenzene, toluene or xylene,

[0178] and the resultant compound of the formula (6a-1) is then reactedwith a primary or secondary amine or piperidine, morpholine, pyrrolidineor piperazine, which may bear one or two substituents selected frommethyl, ethyl and/or phenyl, or with an aqueous ammonia solution,optionally in the presence of solvents, such as for examplemethoxy-ethanol or butanol, optionally with catalysis by, for example, acopper(II) salt at temperatures of 50 to 250° C., preferably of 100 to150° C.

[0179] A process for the production of novel 1,8-naphthalimidederivatives of the formula (7a-1) and (7b-1) (process C),

[0180] in which

[0181] R¹⁴, R¹⁵, R^(49′) and R^(50′) have the above-stated meaning,

[0182] wherein a 1,8-naphthalimide derivative of the formula (IXa andb),

[0183] in which

[0184] R¹⁴, R¹⁵ and R^(11″) have the above range of meaning,

[0185] is produced from a 1,8-naphthalic anhydride of the formula (VIIa)

[0186] in which R^(11″) has the above-stated meaning,

[0187] and an o-phenylenediamine of the formula (X)

[0188] in which R¹⁴ and R¹⁵ have the above-stated meanings, attemperatures of 50 to 250° C., preferably of 90 to 140° C., optionallyin the presence of solvents, such as for example acetic acid, butanol,chlorobenzene, toluene or xylene and the 1,8-naphthalimide derivative ofthe formula (IXa and b) is then reacted with a secondary amine of theformula (XI),

[0189] in which R^(49′) and R^(50′) have the above-stated meaning,

[0190] with catalysis by, for example, a copper(II) salt at temperaturesof 50 to 250° C., preferably of 100 to 150° C., optionally in thepresence of a solvent, such as for example methoxyethanol or butanol.

[0191] When performing the process a) according to the invention for theproduction of the 1,8-naphthalimide derivatives of the formula (6a), 1to 1.8 mol, preferably 1.2 to 1.4 mol of primary amine of the formula(VIII) are generally used per mol of compound of the formula (VII).

[0192] When performing the process b) according to the invention for theproduction of the 1,8-naphthalimide derivatives of the formula (6a-1), Ito 1.8 mol, preferably 1.2 to 1.4 of the primary amine of the formula(VIII) are generally used per mol of compound of the formula (VIIa) and1.2 to 5 mol, preferably 2 to 2.5 mol of the corresponding primary,secondary or cyclic amine are use per mol of compound of the formula(6a-1).

[0193] Production of the 1,8-naphthalimide derivatives of the formula(6a), processes (a) and (b), according to the invention is illustratedby way of example by the following reaction scheme:

[0194] In this scheme, the 4-chloro-N-hydroxyethyl-1,8-naphthalimide isfirst produced by the reaction of 4-chloronaphthalic anhydride and2-aminoethanol. The 4-chloro-N-hydroxyethyl-1,8-naphthalimide is thencombined with piperidine in the presence of a catalytic quantity of acopper(II) salt to form the desiredN-hydroxyethyl-4-piperidino-1,8-naphthalimide.

[0195] When performing the process C) according to the invention for theproduction of the 1,8-naphthalimide derivatives of the formula (7a-1)and (7b-1), 1 to 1.8 mol, preferably 1.2 to 1.4 mol of theo-phenylenediamine of the formula (X) are generally used per mol ofcompound of the formula (VIIa) and 1.2 to 5 mol, preferably 2 to 2.5 molof the secondary amine of the formula (XI) per mol of compound (IXa-b).

[0196] Production of the 1,8-naphthalimide derivatives according to theinvention of the formulae (7a-1 and 7b-1) is illustrated by way ofexample by the following reaction scheme:

[0197] In this scheme, the4/5-chloro-1,8-naphthoylene-1′,2′-benzimidazole, which occurs as anisomeric mixture (approximately 3:1), is first produced by the reactionof 4-chloronaphthalic anhydride and o-phenylenediamine. The4/5-chloro-1,8-naphthoylene-1′,2′-benzimidazole is then combined with2-(methylamino)ethanol in the presence of a catalytic quantity of acopper(II) salt to form the desired4/5-(N-methyl-N-hydroxyethyl)amino-1,8-naphthoylene-1′,2′-benzimidazole.

[0198] The starting products of the formulae (VII), (VIII), (VIIa), (X)and (XI) for the production of the compounds according to the inventionof the formula are compounds which are generally known in organicchemistry.

[0199] The styrene and acrylic acid derivatives of the formulae (22) and(23) which are also necessary for the production of the (co)polymersaccording to the invention are generally known compounds.

[0200] The (co)polymers according to the invention are distinguished bytheir luminescent properties and film-forming capacity and may beapplied onto suitable substrates by casting, knife coating or spincoating. The products exhibit photoluminescence on irradiation both insolutions and as films. The (co)polymers of the present invention aresuitable for the production of electroluminescent displays.

[0201] The invention thus relates to the use of the (co)polymersdescribed above in the luminescent layer of an electroluminescentdevice, which is characterised in that

[0202] an electroluminescent layer is located between two electrodes,

[0203] at least one of the two electrodes is transparent in the visiblerange of the spectrum,

[0204] light in the frequency range of 200 to 2000 nm is emitted when adirect voltage in the range of 0.1 to 100 volts is applied,

[0205] one or more interlayers may additionally be arranged between theelectroluminescent layer and the electrodes.

[0206] These interlayers are known from the literature (c.f. Appl. Phys.Lett., 57, 531 (1990)) and are described therein as HTL (hole transportlayer) and ETL (electron transport layer). The purpose of suchinterlayers is inter alia to increase the intensity ofelectroluminescence.

[0207] The electroluminescent polymers according to the invention mayalso be used in the electroluminescent layer as a mixture with eachother or with at least one further material. This further material maybe an inert binder, charge transporting substances as described in EP-A532 798 or EP-A 564 224, or mixture of inert binders and chargetransporting substances.

[0208] The mixtures of the polymers according to the invention and afurther material are distinguished inter alia that they are film-formingand may be applied in large areas onto suitable substrates by casting,knife coating or spin coating. Suitable substrates are transparentsupports such as glass or plastic films (for example polyester, such aspolyethylene terephthalate or polyethylene naphthalate, polycarbonate,polysulphone, polyimide films).

[0209] The inert binder preferably comprises soluble, transparentpolymers, such as for example polycarbonates, polystyrene,polyvinylpyridine, polymethylphenylsiloxane and polystyrene copolymerssuch as SAN, polysulphones, polyacrylates, polyvinylcarbazole, polymersand copolymers of vinyl acetate and vinyl alcohol.

EXAMPLES Example 1

[0210] 1. Production of3-(6-hydroxyhexoxycarbonyl)-7-diethylaminocoumarin, formula (24) in thereaction scheme

[0211] A solution of bis-(6-hydroxyhexyl) malonate in 1,6-hexanediol isprepared by heating a mixture of 21.6 g (0.15 mol) of Meldrums acid, 59g (0.50 mol) of 1,6-hexanediol and 0.28 g (1.5 mmol) ofp-toluene-sulphonic acid monohydrate for 2 hours at 140° C.

[0212] The resultant solution is then combined with 26.0 g (0.135 mol)of 4-diethylaminosalicylic aldehyde, 0.7 ml of piperidine and 0.1 ml ofacetic acid. The reaction mixture is stirred for 3 hours at 110° C. and,once cool, combined with 300 ml of water. The suspension is extractedwith dichloromethane. The organic phase is evaporated and the residuerecrystallised from toluene.

[0213] 40.2 g (83% of theoretical) of3-(6-hydroxyhexoxy-carbonyl)-7-diethylaminocoumarin are obtained asyellow crystals with a melting point of 85 to 86° C.

[0214] 2. Production of the3-(6-methacryloxyhexoxycarbonyl)-7-diethylaminocoumarin, formula (26) inthe reaction scheme

[0215] 8.36 g (0.08 mol) of methacryloyl chloride (25) are addeddropwise with stirring and cooling with iced water to a solution of 16.3g (0.045 mol) of 3-(6-hydroxyhexoxycarbonyl)-7-diethylaminocoumarin (24)and 10.0 g (0.10 mol) of freshly distilled triethylamine in 50 ml of drytetrahydrofuran. The reaction mixture is stirred for 5 hours at roomtemperature. The reaction mixture is then treated with 200 ml of waterand 200 ml of methylene chloride. Once the phases have separated, theaqueous phase is extracted twice more with 100 ml portions of methylenechloride. The combined organic extracts are washed until neutral anddried with sodium sulphate. Once the solvent has been removed by vacuumdistillation, the residue is adsorptively filtered through a shortsilica gel column with diethyl ether as the mobile solvent. Once thesolvent has been removed by distillation, 17.6 g (92% of theoretical) ofa pale yellow oil are obtained.

[0216] 3. Production of the copolymer according to formula (28) in thereaction scheme with x=13 mol.%, y=87 mol.%

[0217] A solution of 5.0 g (0.012 mol) of3-(6-methacryloxy-hexoxycarbonyl)-7-diethylaminocoumarin (26), 10.0 g(0.078 mol) of n-butyl acrylate (27) and 0.15 g (0.91 mmol) of AIBN in80 ml of dry chlorobenzene are degassed under a vacuum and then stirredfor 3 hours at 100° C under nitrogen. The polymerisation mixture is thenreinitiated with 0.15 g (0.91 mmol) of AIBN in three portions within 3hours. The solution is then added dropwise to 100 ml of methanol withstirring and the suspension is then suction filtered. The crude productis precipitated twice more from a methylene chloride/methanol mixture.Yield 12.7 g (85% of theoretical).

Example 2

[0218] 1. Production of N-(m/p-vinylbenzyl)phenothiazine, formula (31)

[0219] 100 ml of 45% sodium hydroxide solution is added with stirring at0° C. to a mixture of 20 g (0.10 mol) of phenothiazine (29), 18.4 g(0.12 mol) of m/p-vinylbenzyl chloride (30) and 3.39 g (0.01 mol) oftributylammonium hydrogen sulphite in 100 ml of isobutyl methyl ketone.The reaction mixture is vigorously stirred for 4 hours at roomtemperature and then diluted with 100 ml of water and 150 ml of isobutylmethyl ketone. Once the phases have separated, the organic solution iswashed until neutral and dried with sodium sulphate. The solution isthen adsorptively filtered through a short silica gel column withdiethyl ether as the mobile solvent. Once the solvent has been removed,30 g (95% of theoretical) of a pale yellow oil are obtained.

[0220] 2. Production of the copolymer of the formula (33), with x=28mol. %, y=72 mol. %

[0221] 8.0 g (80% of theoretical) of the copolymer (33) may be producedin a similar manner to the method described in example 1 from 5.0 g(0.016 mol) of N-(m/p-vinylbenzyl)phenothiazine (31), 5.0 g (0.042 mol)of m/p-methylstyrene (32) and a total of 0.15 g (0.91 mmol) of AIBN withtoluene as the solvent.

Example 3

[0222] 1.4/5-(N-methyl-N-hydroxyethyl)amino-1,8-naphthoylene-1′,2′-benzimidazoleis obtained in a similar manner to example 5, section 1 from4/5-chloro-1,8-naphthoylene-1,2-benzimidazole in an 82% yield asred-brown crystals of a melting point of 168-169° C.

[0223] 2. Production of4/5-(N-methyl-N-methacryloxethyl)amino-1,8-naphthoylene-1′,2′-benzimidazole,formula (35)

[0224] 6.3 g (90% of theoretical) of the methacrylate (35) are producedin a similar manner to the process described in example I starting from5.83 g (0.017 mol) of4/5-(N-methyl-N-hydroxyethyl)amino-1,8-naphthoylene-1′,2′-benzimidazole(34) and 3.24 g (0.031 mol) of methacryloyl chloride (25). The reactionmixture is worked up by treatment with water and the resultantsuspension is suction filtered. The crude product is recrystallised fromtoluene at low temperature.

[0225] 3. Production of the copolymer according to formula (37), inwhich x=55 mol. %, y=45 mol. %

[0226] In a similar manner to the method described in example 1, 4.8 g(87% of theoretical) of the copolymer (37) may be produced from 4.0 g(9.7 mmol) of4/5-(N-methyl-N-methacryloxyethyl)amino-1,8-naphthoylene-1′2′-benzimidazole(35), 1.5 g (7.8 mmol) of N-vinylcarbazole (36) and a total of 50 mg(0.30 mmol) of AIBN with chlorobenzene as the solvent.

Example 4

[0227] 1. N-isoamyl-4-(N-methyl-N-hydroxyethyl)amino-1,8-naphthalamide

[0228] is obtained in a similar manner to example 5, section I from4-chloro-N-isoamyl-1,8-naphthalimide and 2-(methylamino)ethanol in a 71%yield as yellow to brown crystals of a melting point of 117-118° C.

[0229] 2. Production of theN-isoamyl-4-(N-methyl-N-m/p-vinylbenzyloxyethyl)-amino-1,8-naphthalimide(39)

[0230] A solution of 10.2 g (0.03 mol) ofN-isoamyl-4-(N-methyl-N-hydroxy-ethyl)amino-1,8-naphthalimide (38) in 30ml of dry tetrahydrofuran is added dropwise under nitrogen at 5° C to astirred solution of 4.0 g (0.036 mol) of potassium tert.-butylate in 40ml of dry tetrahydrofuran. The mixture is stirred for a further 5 hoursat room temperature. 5.0 g (0.033 mol) of m/p-vinylbenzyl chloride (30)are then added dropwise at room temperature to the red-brown colouredsolution. After 3 hours, the reaction mixture is treated with 200 ml ofwater and 300 ml of methylene chloride. Once the phases have separated,the aqueous phase is extracted twice more with 100 ml portions ofmethylene chloride. The combined organic extracts are washed untilneutral and dried with sodium sulphate. Once the solvent has beenremoved by vacuum distillation, the residue is adsorptively filteredthrough a short silica gel column with diispropyl ether as the mobilesolvent, wherein an initial run with a small quantity ofmip-vinyl-benzyl chloride is removed. Once the solvent has been removedby distillation, 9.6 g (70% of theoretical) of a yellow oil areobtained.

[0231] 3. Production of the homopolymer according to formula (40)

[0232] In a similar manner to the method described in example 1, 2.3 g(77% of theoretical) of the homopolymer (40) may be produced from 3.0 g(6.6 mmol) ofN-isoamyl-4-(N′-methyl-N-m/p-vinylbenzyloxyethyl)-amino-1,8-naphthalimide(39) and a total of 30 mg (0.18 mmol) of AIBN with toluene as thesolvent.

[0233] 4. Production of the electroluminescent device

[0234] ITO-coated glass (manufactured by Balzers) is cut into substratesof dimensions 20×30 mm and cleaned. Cleaning is performed in thefollowing sequence of stages:

[0235] 1. 15 minutes rinsing in distilled water and Falterol inultrasound bath,

[0236] 2. 2×15 minutes' rinsing in ultrasound bath, each time with freshdistilled water,

[0237] 3. 15 minutes rinsing with ethanol in ultrasound bath,

[0238] 4. 2×15 minutes rinsing in ultrasound bath, each time with freshacetone,

[0239] 5. drying on lint-free lens cleaning cloths.

[0240] A 1% solution of the polymer according to formula (40) (example4) in 1,2-dichloroethane is filtered (0.2 μm filter, Sartorius). Thefiltered solution is distributed on the ITO glass with a spin coater at1000 rpm. The thickness of the dry film is 110 nm and the R_(a) value ofthe surface is 5 nm (Alpha-Step 200 stylus profilometer from TencorInst.).

[0241] The film produced in this manner is then provided with Alelectrodes by vapour deposition. To this end, isolated 3 mm diameterdots of Al are vapour-deposited onto the film using a perforated mask. Apressure of below 10-5 mbar prevails in the vapour deposition device(Leybold) during deposition.

[0242] The ITO layer and the Al electrode are connected to an electricalsupply via electrical supply lines. When the voltage is increased, anelectric current flows through the device and the described layerelectroluminesces. Electroluminescence is in the yellow/green range ofthe spectrum and occurs with an ITO contact of positive polarity.

Example 5

[0243] 1. Production of N-hydroxyethyl-4-piperidinyl-1,8-naphthalimide

[0244] A mixture of 20.0 g (0.073 mol) of4-chloro-N-hydroxyethyl-1,8-naphthalimide, 25.8 g (0.30 mol) ofpiperidine, 2.0 g of copper(II) sulphate and 200 ml of ethylene glycolmonomethyl ether is refluxed for 2 hours while being stirred. Thesolution is cooled to room temperature and then combined with 1 liter ofwater. The suspension is extracted with dichloromethane. The organicphase is evaporated and the residue recrystallised from toluene. 16 g(68% of theoretical) of brown crystals of a melting point of 152-153° C.are obtained.

[0245] 2. Production ofN-(m/p-vinylbenyloxyethyl)-4-piperidyl-1,8-naphthalimide, formula (42)

[0246] In a similar manner to the method described in example 4, 6.4 g(73% of theoretical) of N-(m/p-vinylbenzyl-oxyethyl)-4-piperidyl-1,8-naphthalimide (42) may be produced from 6.48 g (0.020 mol) ofN-hydroxyethyl-4-piperidyl-1,8-naphthalimide (41) and 3.6 g (0.024 mol)of m/p-vinylbenzyl chloride (30).

[0247] 3. Production of the copolymer of the formula (44) with x=1.2mol.% and y=98.8 mol.%

[0248] In a similar manner to the method described in example 1, 2.5 g(79% of theoretical) of the copolymer (44) may be produced from 0.16 g(0.36 mmol) of N-(m/p-vinylbenzyloxyethyl)-4-piperidyl-1,8-naphthalimide(42), 3.0 g (28.8 mmol) of styrene (43) and a total of 30 mg (0.18 mmol)of AIBN with toluene as the solvent.

Example 6

[0249] 1. Production of the copolymer of the formula (45) with x=1 mol.% and y=99 mol. %

[0250] In a similar manner to the method described in example 1, 4.15 g(96% of theoretical) of the copolymer (45) may be produced from 0.10 g(0.22 mmol) ofN-isoamyl-4-(N-methyl-N-m/p-vinylbenzyloxyethyl)amino-1,8-naphthalimide(39), 4.20 g (21.8 mmol) of N-vinyl-carbazole (36) and a total of 30 mg(0.18 mmol) of AIBN with toluene as the solvent.

[0251] 2. Production of an electroluminescent device

[0252] Production process as described in example 4. The dry filmthickness of the copolymer of the formula (45) is 144 nm and the R_(a)value of the surface is 12 nm. Electroluminescence is in theyellow-green range of the spectrum.

1. (Co)polymers which contain at least one repeat chain unit of thegeneral formula (1) or (2) and optionally contain repeat units of thegeneral formula (3)

in which R¹, R² and R³ mutually independently mean hydrogen or C₁-C₆alkyl, M denotes CN or C₁-C₃₀ alkoxycarbonyl, C₁-C₃₀(di)alkyl-aminocarbonyl, C₁-C₃₀ alkylcarbonyl, which may each besubstituted by hydroxy or C₁-C₆ alkoxycarbonyl and furthermore denotesphenyl, naphthyl, anthracenyl, pyridyl or carbazolyl, which may each besubstituted by residues from the group halogen, hydroxy, silyl, C₁-C₃₀alkyl, C₆-C₁₈ aryl, C₁-C₃₀ alkoxy, C₁-C₃₀ alkoxycarbonyl, C₁-C₃₀ acyloxyand C₁-C₃₀ alkylcarbonyl, L¹ and L² mean a photoluminescent residue,wherein the proportion of structural units of the formulae (1) and/or(2) is in each case 0.5 to 100 mol.%, and (3) 0 to 99.5 mol.%, and themolar percentages add up to
 100. 2. (Co)polymers according to claim 1 ,wherein L¹ and L² mutually independently denote a photoluminescentresidue which is based on the skeleton of a fluorescent dye which isselected from the group of coumarins of the formula (4)

pyrenes of the formula (5)

1,8-naphthalimides of the formula (6)

1,8-naphthaloylene-1,2-benzimidazoles of the formulae (7a) and (7b)

phenothiazines or phenoxazines of the formula (8)

with X=O or S, benzopyrones of the formula (9)

carbazoles, fluorenes, dibenzothiophenes and -furans of the formula (10)

with X²=NR²³, CH₂, S or O, wherein R²³ denotes hydrogen or C₁-C₆ alkyl,oxazoles, 1,3,4-oxadiazoles of the formula (1I)

with X³=CH or N benzoquinolines of the formula (12)

9,10-bis-(phenylethynyl)anthracenes of the formula (13)

fluorones of the formula (14)

9,10-diphenylanthracene of the formula (15)

2-styrylbenzazole of the formula (16)

with X⁴=O, S, Se or CH₂, wherein R⁴ denotes hydrogen, C₁-C₃₀ alkyl,C₆-C₁₈ aryl, C₇-C₂₄ aralkyl or C₁-C₃₀ alkoxy or

wherein R⁴³ and R⁴⁴ mutually independently denote hydrogen, C₁-C₃₀alkyl, C₆-C₁₈ aryl, C₇-C₂₄ aralkyl, which may each be substituted byhydroxy, amino, carboxy or C₁-C₄ alkoxycarbonyl, or R⁴³ and R⁴⁴,together with the nitrogen atom to which they are attached, may mean amorpholine, piperidine, pyrrolidine or piperazine ring, which may bearone or two substituents from the group methyl, ethyl and phenyl, R⁵denotes hydrogen, cyano, C₁-C₃₀ alkyl, C₆-C₁8 aryl, C₇-C₂₄ aralkyl,C₁-C₃₀ alkoxy, C₂-C,₂ acyl, C₁-C₁₂ alkoxycarbonyl, C₁-C₁₂(di)-alkylaminocarbonyl, R⁶ denotes hydrogen, cyano, C₁-C₃₀ alkyl,C₆-Cl8 aryl, C₇-C₂₄ aralkyl, C₁-C₃₀ alkoxy or

wherein Z denotes a group OR⁴⁵ or

and R⁴⁵, R⁴⁶ and R⁴⁷ mutually independently denote C₁-C₃₀ alkyl, C₆-C₁₈aryl or C₇-C₂₄ aralkyl, wherein the aromatic rings may additionally befurther substituted by halogen, C₁-C₆ alkyl, C₁-C₆ alkoxy, R⁷, R⁵ and R⁹mutually independently mean hydrogen, C₁-C₃₀ alkyl, C₆-C₁₈ aryl, C₇-C₂₄aralkyl, C₁-C₃₀ alkoxy, cyano, C₂-C₁₂ alkoxycarbonyl, C₁-C₁₂(di)alkylaminocarbonyl or an amino group with one or two C₁-C₆ alkylgroups, R¹⁰ means hydrogen, cyano, C₁-C₃₀ alkyl, C₆-Cl, aryl, C₇-C₂₄aralkyl, C₁-C₃₀ alkoxy, amino, an amino group with one or two C₁-C₆alkyl groups, C₂-C₁₂ acyl, C₁-C₁₂ alkoxycarbonyl, C₁-C₁₂(di)alkylaminocarbonyl, R¹¹ denotes hydrogen, halogen, nitro, C₁-C₄alkoxycarbonyl, C₁-C₄ acyl, C₈-C₂₄ aralkenyl, unsubstituted amino, oramino identically or differently mono- or disubstituted by C₁-C₃₀ alkyl,C₆-C₁₈ aryl or C₇-C₂₄ aralkyl, R¹¹ furthermore denotes morpholinyl,piperidinyl, pyrrolidinyl or piperazinyl, which may bear one or twosubstituents selected from methyl, ethyl and/or phenyl, R¹² denoteshydrogen, C₁-C₃₀ alkyl, C₆-C₁₈ aryl, C₇-C₂₄ aralkyl or C₁-C₃₀ alkoxy,R¹³ denotes hydrogen, C₁-C₃₀ alkyl, C₆-C₁₈, aryl, C₇-C₂₄ aralkyl, C₁-C₃₀alkoxy or

wherein R⁴⁹ and R⁵⁰ mutually independently denote C₁-C₃₀ alkyl, C₆-C₁₈aryl, C₇-C₂₄ aralkyl or R⁴⁹ and R⁵⁰, together with the nitrogen atom towhich they are attached, moreover denote a morpholinyl, piperidinyl,pyrrolidinyl or piperazinyl, which may bear one or two identical ordifferent substituents selected from methyl, ethyl and phenyl, R¹⁴ andR¹⁵ mutually independently mean hydrogen, cyano, halogen, nitro, C₁-C₃₀alkyl, C₁-C₃₀ alkoxy, C₆-C₁₈ aryl or C₇-C₂₄ aralkyl, C₁-C₁₂alkoxycarbonyl, C₂-C₁₂ acyl, C₁-C₁₂ (di)alkylaminocarbonyl, C₁-C₆(di)alkylamino, R¹⁷ means hydrogen, C₁-C₃₀ alkyl, C₆-C₁₈ aryl or C₇-C₂₄aralkyl and R¹⁶, R¹⁸ to R²² and R²⁴ to R⁴⁰ mutually independently meanhydrogen, cyano, C₁-C₃₀ alkyl, C₆-C₁₈ aryl, C₇-C₂₄ aralkyl, C₁-C₃₀alkoxy, an amino group with one or two C₁-C₆ alkyl groups, unsubstitutedamino, C₂-C₁₂ acyl, C₁-C₁₂ alkoxycarbonyl or C₁-C₁₂(di)alkylaminocarbonyl, wherein the aliphatic carbon chains, such as,for example, alkyl, alkoxy, alkylamino, aralkyl, in the residues R⁴ toR¹³, R¹⁶ to R⁴⁰ may be interrupted by one or more, preferably one or twoheteroatoms selected from oxygen, nitrogen and sulphur and/or by one ormore, preferably one or two, phenylene rings, which may be substitutedby C₁-C₄ alkyl and/or halogen, and wherein furthermore the luminophoreis attached to the polymer side chains via an oxygen, a hydroxy orcarboxy group or a nitrogen of an amino or primary amino on theabove-stated substituents.
 3. (Co)polymers according to claim 1 ,wherein the proportion of structural units of the formulae (1) and/or(2) is 0.5 to 60 mol.% and optionally of the formula (3) 40 to 99.5mol.%.
 4. (Co)polymers according to claim 1 , wherein L denotes afluorescent dye selected from the group of coumarins of the formula (4),pyrenes of the formula (5), 1,8-naphthalimides of the formula (6),1,8-naphthoyl-ene-1′,2′-benzimidazoles of the formula (7),phenothiazines or phenoxazines of the formula (8), carbazoles andfluorenes of the formula (10).
 5. Process for the production of(co)polymers of the formula (1) according to claim 1 , wherein monomersof the formula (20) or (21) are produced

from a fluorescent dye functionalised with an OH, COOH or NH group,which dye contains the structure of L, and a styrene or acrylic acidderivative of the formulae (22) and (23)

in which R¹ and R² have the above-stated range of meaning and R⁴¹denotes halogen, R⁴² denotes halogen, a hydroxy or C₁-C₆ alkoxy group,in the presence of a base and these monomers are then polymerised,optionally in the presence of units of the formula (3) as comonomers. 6.Use of the (co)polymers of the formula (1) according to claim 1 for theproduction of electroluminescent devices.
 7. Electroluminescent devicewhich contains (co)polymers according to claim 1 as theelectroluminescent substance.
 8. Electroluminescent device according toclaim 7 containing two electrodes, between which is located anelectroluminescent layer, which contain the (co)polymers as theelectroluminescent layer, and wherein one or more interlayers may bearranged between the electroluminescent layer and the electrodes.